IR 05000219/1986016

Insp Rept 50-219/86-16 on 860603-06.No Violation Identified. Major Areas Inspected:Nonradiological Chemistry Program, Including Measurement Control & Analytical Procedure Evaluations

ML20202D499
Person / Time
Site:	Oyster Creek
Issue date:	07/03/1986
From:	Pasciak W, Rabatin K, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20202D470	List: IR 05000219/1986016 ML20202D466
References
50-219-86-16, NUDOCS 8607140146
Download: ML20202D499 (6)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report N /86-16 Docket N License N DPR-16 Category C Licensee: GPU Nuclear Corp 100 Interpace Parkway Parsippany, New Jersey 07054 Facility Name: Oyster Creek Nuclear Generating Station Inspection At: Forked River, New Jersey Inspection Conducted: June 3-6, 1986 I

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wh l Inspectors: , 4. . @ gab 7/ 7/$ (-

Ff. Zibd isky,' Chemist /dati luL d. /k , kin K. Rabatin, R tion Specialist pat 6

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Approved by: / fk . 9"") W m .

T.J.(Pbsciak, Chief, EffluentY Raciation j bb Protedtion Section, DRSS hatfe Inspection Summary: Inspection on June 3-6, 1986 (Report No.50-219/86-16)

Areas Inspected: Routine, announced inspection of the nonradiological chemistry program. Areas reviewed included measurement control and analytical procedure evaluation Results: No violations were identifie %f a

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DETAILS Individuals Contacted

• J. Barton, Deputy Director

• C. Halbfoster, Manager, Plant Chemistry

• R. Hillman, Senior Chemist

• Dunphy, Senior Chemist

• B. Holman, Licensing Engineer P. Fiedler, Vice President and Director J. Sullivan, Director, Plant Operations E. Donner, Licensing C. Hager, Plant Engineer

• Denotes those present at the exit intervie The inspector also interviewed other licensee employees including members of the chemistry staf . Action on Previous Licensee Findings (0 pen) 25-00-13 TI-The inspection covered part of this item. Of the two

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modules included in the TI, Module 79501 was complete . Measurement Control Evaluation The licensee's measurement control program will be verified through analysis of actual plant water samples. Samples from the liquid poison tank, closed cooling water, make up system water and condensate were taken and duplicate samples were sent to Brookhaven National Laboratory (BNL)

for independent verification. The licensee will determine boron cons-centration on the liquid poison tank sample, chloride on the closed cool-ing water sample, silica on the make up water sample and metals on the condensate sample. On completion of the analyses by both laboratories, a statistical evaluation will be made (Inspector Follow-up Item 50-219/86-16-01).

The inspectors reviewed the measurement control charts. Some of the acceptance criteria for the analyses were arbitrary 10% without the use of charts. The charts that were generated were for analyst evaluation and used duplicate samples to demonstrate precision and spiked samples to demonstrate accuracy. The control charts did not demonstrate the effici-ency or the trends of the measurement system. The inspectors recommended a 2 sigma alert criteria and a 3 sigma acceptance parameter as was discussed in report number 50-219/84-33. It was also suggested that more control charts be generated for those analytes whose parameters are men-tioned in the fuel warranty and vendor requirements. The licensee agreed to generate the necessary control charts (Inspector Follow-up Item 50-219/86-16-02).

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The inspectors reviewed the nonradiological interlaboratory and intra-laboratory crosscheck programs. These programs are documented in Proce-dure 822.6 " Quality Control: Vendor Laboratories" and Procedure 82 " Quality Control: Analyst Performance". The licensee receives and analyzes nonradiological samples prepared by a vendor laboratory on a quarterly basis. The results are compared to the vendor's known value using statistical methods and predetermined acceptance criteria. Measure-ments in disagreement are documented and investigated by the Lead Chemis The intralaboratory cross check program uses duplicate, standard, and spiked samples prepared by the Lead Chemist to evaluate chemistry tech-nician performance and the analytical methods. These quality control samples are rotated through the technicians' weekly assignments. However, the number of quality control analyses is dependent on the analyte of interest and the sampling' frequenc The Lead Chemist reviews the results of these analyses and investigates any out of control measure-ments. As discussed above, the data is plotted on accuracy and precision control charts. Data and control charts from the interlaboratory and intralaboratory programs are documented in the Oyster Creek Chemistry Group Quality Control Repor The inspectors observed that the licensee used one standard stock solution for calibration and control solutions. Maintenance of two standard stock solutions is needed to provide an analytical cross check on the cortinuing quality of the stock solutions. The licensee agreed to maintain two standard stock solution The calibration curves were not statistically fit to the data points but were graphically approximated. This could produce as much as 15 percent error as may have been the case in the licensee's analysis of the NRC blind standard for chloride. The licensee agreed to use a statistical method to draw the calibration curve The licensee wasn't using the control standard solutions in the same concentration range as the samples. The standard solution concentrations were as much as ten times the expected sample quantity. This prevented the licensee in identifying any anomaly associated with low concentrations of the analyte. The licensee agreed to use an accropriate concentration for the control standards when the new control charts are generate . Analytical Procedures Evaluation During the inspection, standard chemical solutions were submitted by the inspector to the licensee for analysi The standard solutions were prepared by BNL for NRC Region 1, and were analyzed by the licensee using normal methods and equipment. The analysis of standards is used to verify the various plant systems witn respect to Technical Specification and other regulatory requirements. In addition, the analysis of standards is used to evaluate the licensee's analytical procedures with respected to accuracy and precisio ^

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The results of the standard measurements comparison indicated that seven out of twenty-one comparisons were in disagreement under the criteria used for comparing results (see Attachment 1). The spectrophotometric chloride disagreements were due to the licensee graphically approximating the data points on the calibration curve instead of statistically fitting the curv The ion chromatography chloride disagreement was due to statis-tics. The iron disagreement was due to the NRC standard being less than the licensee's lowest standard and as a result the extrapolation intro-duced error. The nickel and copper disagreements were on the conservative side and equaled to less than 7%. The boron disagreement was a sampling erro Because the measurement program lacked the control charts with the 2 sigma and i 3 sigma and a single standard stock solution was used, it was difficult to pinpoint the cause of the measurement disagreement The licensee is using upgraded analytical procedures and state-of-the-art instrumentation in the laboratory. When the recommendations are incor-porated into their measurement systems, the licensee should have an effective measurement progra .

5. Exit Interview The inspectors met with the licensee representatives (denoted in paragraph 1) at the conclusion of the inspection on June 6, 1986, and summarized the scope and findings of the inspection. At no time during this inspection was written material provided to the licensee by the inspectors.

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ATTACllMENT 1 ,

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Criteria For Comparing Analytical Measurements This attachment provides criteria for comparing results of capability teit In these criteria the judgement limits are based on the uncertainty of the ratio of the licensee's value to the NRC value. The following steps are performed:

(1) the ratio of the licensee's value to the NRC value is computed Licensee Value (ratio = NRC Value );

(2) the uncertainty of the ratio is propagate If the absolute value of one minus the ratio is less than or equal to twice the ratio uncertainty, the results are in agreemen (ll-ratial 2 2 uncertainty)

ZsE, then Sz2 = Sx2 + syz Y x2 72 y2 (From: Bevington, P. R. , Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York,1969)

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Capability Test Results Oyster Creek Nuclear Generating Station Chemical Ratio Parameter NRC Value Lic. Value (Lic. /NRC) Comparison Results in parts per billion (ppb)

Chloride 103 7 72 3 0.70 0.06 Disagreement (Spectrophotometry) 697 30 663 6 0.95 0.04 Agreement 277 3 267 3 0.96 0.02 Disagreement Chloride 5.15 0.04 5.59 0.17 1.08 0.03 Disagreement (Ion Chromatograph) 6.97 0.30 7.10 0.20 1.02 0.05 Agreement 2.77 0.28 3.29 0.01 1.19 0.12 Agreement Results in parts per million (ppm)

Boron 1014 15 994 1 0.98 0.01 Agreement 3047 26 2927 13 0.96 0.01 Disagreement 5040 130 4885 0 0.97 0.03 Agreement Nickel 1,32 0.16 1.27 0.01 0.96 0.12 Agreement 3.79 0.07 3.9810.05 1.05 0.02 Disagreement 2.58 0.13 2.64 0.07 1.02 0.06 Agreement Iron 1.28 0.09 1.04 0.03 0.81 0.06 Disagreement 3.43 0.21 3.72 0.06 1.08 0.07 Agreement 2.3910.10 2.46 0.01 1.03 0.04 Agreement Copper 1.33 0.01 1.35 0.02 1.02 0.01 Agreement 3.84 0.04- 4.12 0.06 1.07 0.02 Disagreement 2.60 0.04 2.71 0.02 1.04 0.02 Agreement Chromium 1.20 0.10 1.28 0.02 1.07 0.09 Agreement l 3.74 0.28 3.88 0.05 1.04 0.08 Agreement 2.69 0.05 2.58 0.01 0.96 0.02 Agreement